Diazine derivatives



Patented July 13, 1943 DIAZINE DERIVATIVES Gaetano F. DAlelio, Pittsfleld; Mass., assignor to General Electric Company, a corporation of New York No Drawing. Application February 28, 1942, Serial No. 432,895

- 16 Claims.

This invention relates to new chemical compounds and more particularly to diazine derivatives. The invention especially is concerned with the production of new and useful compounds corresponding to the following general formula:

Where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon andsubstituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals, R represents a member of the class consisting .of divalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals, and X represents a halogen atom, more particularly chlorine, bromine, fluorine or iodine. These compounds are (diamino pyrimidyl thio aliphatic-amido or aliphatic-thionoamido) (halogeno aliphatic-amide or aliphatic-thionoamido) (derivatives of divalent hydrocarbons.

Illustrative examples of monovalent radicals that R in the above formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyl, methallyl, ethallyl, crotyl, etc., including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.); aryl (e. g., .phenyl, diphenyl or xenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2-butenylphenyl, tertiary-butylphenyl, etc.); aryl-substituted aliphatic (e. g., benzyl, phenylethyl, phenylisopropyl, cinnamyl, etc.) and their homologues, as well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen. Specific examples of halogeno-substituted hydrocarbon radicals are chloromethyl, chloroethyl,

chlorophenyl, dichlorophenyl, chlorocyciohexyl, ethyl chlorophenyl, phenyl chloroethyl, bromoethyl, bromopropyl, fiuorophenyl, iodophenyl, bromotolyl, etc. Preferably R in Formula I is hydrogen. However, there also may be produced phenylene,

in accordance with the present invention compounds such, for instance, as those represented by the general formulas and, more particularly,

as given above with reference to Formula I,

Illustrative examples of divalent radicals that R. in the above formulas may represent are:

butyl 2,4-naphthylene, etc.; divalent aromaticsubstituted aliphatic, e. g., phenylethylene, phenlypropylene, naphthylisobutylene, xylylene, a1- pha-(4-toly1ene) betel-butyl, etc.; radicals that may be classed. either as divalent aliphatic-substituted aromatic or divalent aromatic-substitutedaliphatic, e. g., 4. alpha-'tolylene, 3, betaphenyleneethyl, 4, alpha-xylyiene, 2, gammaphenylene-butyl, etc.; and their homologues, as well as those divalent radicals with one or more. of their hydrogen atoms replaced by a substituent, e. g., halogeno, amino, acetyl, acetoxy, carboalkoxy,.alkoxy, aryloxy, hydroxy, alkyl, alkenyl, etc. Specific examples of substituted divalent radicals are' chloroethylene, chloropropylene, bromobutylene, chlorophenylene, chlorotolylene, bromophenylene, chloronaphthylene, bromonaphthylene, bromo 1,4-tolylene, chlorocyclopentylene, chlorocyclopentenylene, carbomethoxyethoxyphenylene, acetophenylene, acetoxyphenylene, bromocyclopentylene, aminophenylene, phenoxyphenylene, methylphenylene (tolylene), allylphe'nyleneetc. Preferably R is ethylene. phenylene or tolylene.

The new compounds of this invention may be used, for example, as pharmaceuticals, plasticizers, fungicides, insecticides, as an intermediate in the preparation of dyes and other chemical compounds, for instance as an intermediate in producing derivatives thereof such as ureido, ydrazino, carbamyl amidine, methyl'ol, etc., de-

Bis-(N-methyl alphabromopropanamidoi propenes Bis-(beta-iodopropanamido) butanes rivatives. These new compounds are especially,

a valuable in the preparation of synthetic resinous assign'ee as the present invention. These newcompounds also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

More specific examples of the chemical compounds of this invention are the (diamino py= rimidyl thio acetamido) (halogeno acetamido)- substituted aliphatic hydrocarbons, more particularly the (diamino pyrimidyl thio acetamido) (halogeno acetamido) aikanes, e. g., alpha-(4,6- diamino pyrimidyl-2' thio acetamido) beta-(chloroacetamidol ethane, alpha-(2,4-diamino pyrimidyl-6 thio acetamido) beta-(chloroacetamido) ethane, the alpha-(diamino pyrimidyl thio acetothionoamido) beta (chloroacetothionoamidoi ethanes, the (diamino pyrimidyl thio acetamido) (halogeno acetamido)-substituted aromatic hydrocarbons, e. g., the (diamino pyrimidyl thio acetamido) (halogeno acetamido) benzenes, the (diamino pyrimidyl thio acetothionoamido) (halogeno acetothionoamido) benzenes, the (diaminq pyrimidyl thio acetamido) (halogeno acetamido) toluenes, etc.

Various methods may beemployed to produce the chemical compounds with which this invention is concerned. I prefer to prepare them by efiecting reaction between a bis-(halogeno aliphatic-amide) -substituted divalent compound or a bis-(halogeno aliphatic thionoamido) -substi- Bis-(alpha-methyl beta-chloro N-isopropyl propanamido) chloroisobutanes Bis-(alpha-butyl beta-bromo N-ethyl propanamido) pentanes Bis-(alpha-phenyl beta-chloro octanamido) isopentanes Bis-(beta-chlorophenyl beta-bromo N-cyclopentyl butanthionoamido) cyclopentanes Bis-(alpha, alpha-ditolyl beta-chloro propanamido) cyclopentanes Bis-(alpha-xylyl alpha-bromo N-phenyl butanamido) cyclohexanes Bis-(alpha-chlorotolyl alpha-methyl beta-chloro pentanamido) chlorocyclohexenes Bis-(N-tolyl chloroacetothionoamido) cycloheptanes Bis-(beta-bromopropanamido) benzenes Bis-(beta-chloro N-benzyl 4-pentenamido) biphenyls Bis-(bromo'cyclopentyl chloro N-naphthyl acetamido) naphthalenes Bis-(bromoacetamido) ethane, more particularly alpha, beta-bis-(broinoacetamido) ethane 2,4-bis-(cyclohexenyl biomo acetothionoamido) chlorotoluene H 2,5-bis-(beta-phenyl alpha-chloro N -chlorophen yl propanamido) ethylbenzene 3,4 bis -(beta bromopropanamido) propyibenzene 4,4'-bis-(N-bromoethyl chloroacetamido) diphenylmethane 2,4 bis (cyclopentenyl chloro N aminophenyl acetamido) l-isobutyl naphthalene Bis-(fluoroacetamido) benzenes Alpha, beta bis-(omega-chloro alpha-.brcrho N butylphenyl pentanamido) phenylethane Bis-(bromoacetamido) propanes Bis-fbromoacetamido) butanes' Bis-(bromoacetamido) benzenes Bis-(bromoacetamido) toluenes tuted divalent compound and a mercapto diami-,

;no pyrimidine in the presence of a hydrohalide acceptor, the reactants being employed inthe ratio of one mol of the mercapto diamino pyrimidine per mol of the said substituted divalent compound. Illustrative examples of substituted divalent compounds that may be used, depending on the end-product desired, are:

,2-toluido 4-mercapto G-methylamino pyrimidine Y Illustrative examples of diamino mercapto pyrimidines that may be employed. depending upon the particular end-product sought; are:

2'-mercapt0 4,6-diamino pyrimidine 4-mercapto.2,6-diamino pyrimidine 2-mercapto 4-bromotoluido fi-benzylamino pyrimidine Z-mercapto 4-phenylchloroethylamino 6 phenethylamino pyrimidine 2-mercapto 4-,chloroanilino fi-ethylphenylamino pyrimidine 2-mercapto 4-cycloheptylamino 6-isopropylamino pyrimidine I 2-mercapto 4,6-diamino '5-methyl pyrimidine 4-mercapto 2,6-diamino 5-methy1 pyrimidine 2-mercapto 4,6-di-(methylamino) pyrimidine 4-mercapto 2,6-di-(methylamino) pyrimidine Z-mercapto 4,6-di-(me.thylamino) 5-methy1 pyrimidine 4-mercapto 2,6-di-(methylamino) 5-phenyl pyrimidine Z-mercapto 4-c-hloroethylamino G-methylamino pyrimidine 2-mercapto 4,6-di-(anilino) pyrimidine 2-mercapto 4,6-di-(ani1ino) 5-butyl pyrimidine Z-mercapto 4-xenylamino 5-cyclopentyl 6-amylcium hydroxide, barium hydroxide; ammonium amino pyrimidine hydroxide, etc.; carbonates of inorganic bases,- 2-toluido 4-mercapto 5-cyclohexeny1 6-amino including the carbonates of alkali metals; organic pyrim ne -t01u1d0 4-amin0 5-cyclohexenyl amines such as tertiary amines, e. g., trimethyl G-mercapto pyrimidine) 5 amine, triethyl amine,'tributy1 amine, pyridine, 2-m rc p o m1 0 y a in0 pyr di dimethyl aniline, quinoline, etc.; quaternary am- 2-mer pto 4,6-di-(pr0py1amino) pyrimidi monium bases, e. g., tetramethyl ammonium hy- 2-allylamino i-mercapto G-chlorophenylamino d nd t and t like,

pyrimidine The reaction between'the mercapto diamino 2-amy a n -m r apt fi-p yl fi-a n P pyrimidine and the bis-(halogeno aliphatic-amiimidine do) or bis-(halogeno aliphatic-thionoamido) -gg g ggg g g ip substituted divalent compound may be carried out in any suitable manner, but preferably et- 'gg ggfi fifg 4'memapto 6'isobutylammo 15 fected in the presence of'a suitable solvent or mixture of solvents. Although various solvents ggg 4 anylammo 6 butyllamipno pynmi and solvent mixtures may be employed, I prefer 2 mercapto 4 (3, buteny1amin) 6 ispmpy1am to use water or a mixture of water and alcohol. mo pyrimidine The reaction may be carried out under a variety 2-mercapto 4-isobutylamino 6-cyclopentylamino temperature and Pressure conditions: for

pyrimidine stance at normal, sub-normal or at elevated tem- Z-mercapto 4-amino fi-chloroxenylamino pyrims d at t sp Sub-atmospheric m i or super-atmospheric pressures. 2-mercapto 4-ethylphenylamino 5-naphthy1 6- The above reaction may be'represented by the xylidino pyrimidine following general equation:

I R 0 \N I r z hydrohal' 0 (RHN) II & SH II I R. acceptor 2 2-mercapto 4-isopropylanilino 5-benzyl (i-benzyl- In the above equation 11, Z, R, R. and K have amino pyrimidine I the same meanings as given above with reference 2-mercapto -phenethylamino 5-(2'-buteny1) 6- to Formula I. I

cyclopentenylamino pyrimidine In order that those skilled in the art better may 2 -mercapto 4,6-diamino fi-bromotolyl pyrimidine understand how the present invention may be Z-mercapto 4-amino S-phenylisopropyl 6-chlorocarried into effect, the following illustrative excyclohexylamino pyrimidine ainples are given. All parts are by weight. Z-mercapto 4-isobuty1amino fi-bromonaphthyl- Example 1 amino pyrimidine gmmmapto 4 m 5..pheny1propy1 pyrimi This example illustrates the preparation. of dine alpha-( 4,6-diamino pyrimidyl-2 thio acetamido) 2-mercapto -chlorobenzylamino 5-ch1orobutyl r beta-(chloroacetamido) ethane, the formula for fi-bromoethylamino pyrimidine do which is 2-mercapto -amino 5-ethylchlorophenyl 6-sec.- v NH:

butylamino pyrimidine 2-mercapto 4-pentylamino 6-cyclohexylamino pyrimidine 'fi f h 2-mercapto 4-n-hexylamino fi-xenylamino pyr- H N-C CSCHzCNH-CHzCH NHC-CH CI imidine Z-mercapto 4-oyclohexenylamino 6-naphthylamino pyrimidine I v 2-mercapto 4-amino 6-bromoethylamino pyrimi- Parts alg -1: 1: dine ratios 2-mercapto -amino G-methylamino pyrimidine z-mercapt-o 1-ami 0 6 ylDheny min0 Z-merca to 4,6-diamino pyrimidine 710 1 Alpha, ta-bis-(chloroacetamido) ethane.-. 106.5 1 pynmldme Sodium hydroxide .0 1 2-mercapto 4-amino 6-benzylamino pyrimidine 6 0 I gfigggg: chlorocyclopentylammo 6 tolmdo The 2-mercapto 4,6-diamino pyrimidine was dissolved in a solution of the stated amount of Various hydrohalide acceptors may be emsodium hydroxide dissolved in 200 parts of we ployed. I prefer to use a hydrolialide acceptor ter, resulting in the formation of the sodium salt that will react ith th mercapto pyrimidine to 7 of the pyrimidine derivative. The bis-(chloroform a water-soluble salt. Examples of such acacetamido) ethane was added to a mixture of ceptors are the alkali-metal hydroxides, e. g., 1,000 parts water and 250 parts alcohol, to which Sodium hydroxide, potassium hydroxide, etc. Adthen was added the solution of the sodium salt of ditional examples of hydrohalid acceptors that the pyrimidinederivative. The resultant'mixmay be used are other inorganic bases, e. g., cal- 7 ture was heated on a steam plate for a short while. A crystalline precipitate .formed on cooling the reaction mass to room temperature. The

precipitate comprising alpha-(4,6-diamino py- I rimidyl-2 thio acetamido) amido) ethane was filtered off, washed free water-soluble salts and then dried.

Example 2 Alpha-(2,6-diamino pyrimidyl-4 thio acetamido) beta-(chloroacetamido) ethane .is prepared in essentially the same manner as debeta-(chloroacetscribed under Example 1 with" the exception that,

instead of 71 parts 2-mercapto 4,6-diamlno pyrimidine, there is used 71-parts o1 '4-mercapto 2,6-diamino pyrimidine.

A Example 3 Alpha-(4,6-diamino pyrimidyl-2 thio acetothionoamido) beta-(chloroacetothionoamido) ethane is prepared in essentially thesarne manner as described under Example 1 with the exception that, instead of alpha, beta-bis-(chloroacet amido) ethane, an equivalent amount of alpha, beta-bis-(chloroacetothionoamido ethane is employed. I

4 Example 4 I A (51,6-diamino pyrimidyl-2 thio acetamido) (chloroacetamido) benzene is produced in essentially the same manner as described under Example 1 with the exception that, instead of alpha,

lent amount or a bis-(chloroacetamido) benzene is used.

. Example 5 A (4,6-diamino pyrimidyl-2 thio acetamido) (chloroacetamido) toluene is produced in essentially the saine' manner as described under Example l with the exception that, instead of alpha, beta-bis-(chloroacetamido) ethane, an equivalent amount ofa bis-(chloroacetamido) toluene is employed.

Example 6 Alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(bromoacetamido) ethane is pre-' pared in essentially the same manner as described under Example 1 with the exception that, instead of alpha, beta-bis-(chloroacetamido) ethane, an equivalent amount of alpha, beta-bis-(bromoac etamido) ethane is used.

Other examples of the new chemical compounds of this invention are listed below: (Diamino pyrimidyl thio acetamido) (chloro- "beta-bis-(chloroacetamido) ethane, an equivaacetamido) propanes, including the-(4,6-di- I amino pyrimidyl-2 thio acetamido) (chloroacetamido) propanes and the (2,6-diamino pyrimidyl-.4 thio acetamido) (chloroacetamido) propanes (Diamino pyrimidyl thio acetothionoamido) (bromoacetothionoamido) propanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) butanes (Diamino pyrimidyl thio acetamido) (iodoacetamido) pentanes (Diamino pyrimidyl thio acetamido) (fluoroa'cetamido) octanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) chlorobutanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) chlorobenzenes (Diamino pyrimidyl thio acetamido) '(bromoacetamido) toluenes (Diamino pyrimidyl thio acetamido) (chloroacetamido) xylenes (Diamino pyrimidyl thioacetamido) (chloroacetamido) naphthalenes (Diamino pyrimidyl thio acetamido) (chloroacetamido) ethyl benzenes (Diamino pyrimidyl thio acetothionoamido) (chloroacetothionoamido) cyclohexanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) butenes (Diamino pyrimidyl thio acetamido) (chloroacetamido) cyclohexenes (Diamino pyrimidyl thio acetamido) (bromoacetamido) bromo-benzenes v (Diamino pyrimidyl thio acetamido) (chloroacetamido) 'chloronaphthalenes Alpha-,(diamino pyrimidyl alpha'-thio propanamido) beta-(alpha"-chloro' propanamido) ethane, including alpha-(4,6-diamino pyrimidyl-2 alpha'-thio propanamido) beta- (alpha"-chloro propanamido) ethane and alpha-(2,6-diamino pyrimidyl-4 alpha'-thio propanamido) beta-(alpha"-chloro propanamido) ethane v Alpha-(diamino pyrimidyl betel-thio propanamido) beta-(beta"- bromo propanamido) ethane, including alpha-,(4,6-diamino py- (Diamino pyrimidyl beta-thio propanamido) (beta'-bromo propanamido) toluenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-iodo propanamido) xylenes (Diamino pyrimidyl beta-thio propanamido) (beta-chloro propanamido) xylenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-fluoro propanamido) ethylbenzenes (Diamino pyrimidyl beta-thio propanamido) (beta'-chloro propanamido) naphthalenes (Diamino. pyrimidyl alpha-thio propanamido) alpha-c hloro propanamido) chioronaphthalenes (Diamino pyrimidyl beta-thio propanamido) (beta-bromo propanamido) bromobenzenes (Diamino pyrimidyl alpha-thio propanamido) (a1pha'-chloro propanamido) chlorcbutanes (Diamino pyrimidyl beta-thio propanamido) (beta'-chloro propanamido) anthracenes (Diamino pyrimidyl alpha-thio propanthionoamido) (alpha-chloro propanthionoamido) benzenes (Diamino pyrimidyl beta-thio propanthionoamido) (beta'-bromo propanthionoamido) toluenes Alpha-(4,6-di-[methylamlno] -methyl pyrimidyl-2 thio methyl N-methyl acetamido) gamma-(methyl N'-methyl bromoacetamido) propene.

(4-chloroethylamino 6-methylamino pyrimidyl- 2 beta-thio propana-mido) (beta'iodo propanamido) butanes 1 (4,6-dl-[anili no] 5-butyl pyrimidyl-2 beta-thlo alpha. methyl N isopropyl propanamido) (alpha'-methy1 beta'-chloro N '-isopropyl 'propanamido) chloroisobutanes (4 xenylamino 5-cyclopentyl G-pentylamino -pyrlmidyl-2 beta-thio alpha-butyl N-ethyl propanamido) (alpha'-butyl beta'-bromo N'- ethyl propanamido) pentanes (2-toluido 4-amino 5-cyclohexenyl pyrimidyl-6 beta-thio beta-methyl beta-chlorophenyl N- cyclopentyl propanthionoamido) (beta/- methyl beta'-chlorophenyl beta'-bromo N'- cyclopentyl' propanthionoamido) cyclopentanes (2-allylamino' 4-amino 5 pheny1 pyrimidyl-6 beta-thio alpha, alpha-ditolyl propanamido) (alpha, alpha'-ditolyl betel-chloro propanamido) cyclopentenes (2-isopentylamino- -4-chlorophenylamin pyrimidyl-6 thio ethyl xylyl acetamido) (ethyl -xy1yl chloroacetamido) cyclohexanes 1 (2-dichloroanilino 4-propylamino 5-tolyl pyrimidyl-6 thio N-tolyl acetothionoamido) N- tolyl chloroacetothionamido) cycloheptanes (2-cyclohexylamino 4-isobutylamino pyrimidyl- 6 beta-thio propanamido) (beta'-bromo propanamido) benzenes (4-chloroxenylamino S-amino pyrimidyl-2 betathio beta-vinyl N-benzyl propanamido) (beta/- vinyl beta'-chloro N'-benzyl propanamido) biphenyls (4-iwlidino S-naphthyl G-ethylanilino pyrimidyl- 2 thio bromocyclopentyl acetamido) (bromocyclopentyl chloro acetamido) naphthalenes 4-(4'-benzylamino 5'-benzy1 6'-isopropy1anilino pyrimidyl-2' thio cyclohexenyl acetothionoamido) Z-(cyclohexenyl bromo acetothionoamido) chlorotoluene 5-(4'-cyclopentenylamino 5'-(2"-butenyl) 6'- phenethylamino pyrimidyl-2' thio benzyl acetamldo) 2-(benzyl chloro acetamido) ethylbenzene 4-(4',6'-diamino 5'-bromotolyl pyrimidyl-2' beta-thio propanamido) 3-(beta'-bromo propanamido) isopropylbenzene (4-chlorocyclohexylamino 5-phenylisopropyl 6- amino pyrimidyl-2 thio acetamido) (chloroacetamido) diphenylmethanes 1-(4'-isobutylamino 6-bromonaphthylamino pyrimidyl-2 thio cyclopentenyl acetamido) 2- cyclopentenyl chloroacetamido) 4-isobuty1 naphthalene Alpha- (4,6-diamino 5-phenylpropyl pyrimidyl-2- thio chloropropyl acetamido) beta-(chloropropyl bromo acetamido) alpha-phenylethane Alpha-(4-chlorobenzylamino 5-chlorobutyl 6- bromoethylamino pyrimidyl-2 thio acetamido) gamma-(chloroacetamido) alpha-phenylpropane s:

It will be understood, of course, by those skilled in the art that, in those compounds listed above that are generically named, the described substituent groupings may be attached to any two positions of the divalent compoundrepresented by R in Formula I. It also will be understood that the expression diamino pyrimidyl" includes,both the 4.6-diamino pyrimidy1-2 and the 2,6-diamino pyrimidyl-4 (2,4-diamino pyrimidyl-fi) derivatives.

In a manner similar to that described above with particular reference to the diamino [(-NHR) 2'] pyrimidine (1,3-diazine) derivatives, corresponding derivatives of the 1,2-diazines and of the 1,4-diazines may be prepared. It also will be understood by those skilled in the art from the foregoing description of the preparation of the diazinyl monosulfides that similar compounds may be prepared in which two or three sulfur linkages are attached to the diazine nucleus.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. Chemical compounds corresponding to the general formula Z Z II II where n represents an integer and is at least 1 and not more than 2, Z represents a member 0! the class consisting of oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halohvdrocarbon radicals, R represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

2. Chemical compounds as in claim 1 wherein R represents hydrogen.

3. Chemical compounds as in claim 1 wherein X represents chlorine.

4. Chemical compounds as in claim 1 wherein R represents hydrogen, Z represents a member of the class consisting of oxygen and sulfur, and

nisl.

5. Chemical compounds as in claim 1 wherein R represents hydrogen, Z represents a member of the class consisting of oxygen and sulfur, n is 1, and X represents chlorine.

6. Chemical compounds corresponding to the general formula I z z III II Ii where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting 01' oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals, R represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

'7. Chemical compounds corresponding to the general formula carbon radica1s.

8. A (diamino pyrimidyl thio acetamldo) (hal'ogeno .acetamido) -substituted aliphatic hydrocarbon.

9. A (diarnino pyrimidyl thio acetamido) (halogeno acetamido) alkane.

10. Alpha-(4,6-diamino pyrimidy1-2 thio acetamido) beta-(chloroacetamido) ethane.

11. A (diamino pyrimidyl thioacetamido) (halogeno acetamido) -substituted aromatic hydrocarbon.

12. A (diamino pyrimidyl thio acetamido) (halogeno acetamido) benzene.

13. A (diamino pyrimidyl thio acetamido) (halogeno acetamido) toluene.

14. The method oi preparing chemical compounds corresponding to the general formula where 11. represents an integer and is at least 1 drogen and monovalent hydrocarbon and halohydrocarbon radicals, R represents a member where R represents a member of the class consisting of divalent hydrocarbon and ha1ohydro-' o! the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals and x represents a halogen atom, said method comprising eflecting reaction, in the presence of a hydrohelidey 5 acceptor; between equimolecular proportions pt, (1) a mercapto pyrimidine corresponding to the general iormula where n Z R, R and K have the meanings above given. j a

15. A method as in claim 14 wherein'the hydrohalide acceptor is an alkali-metal hydroxide.

16. A method oi preparing alpha-(4,6-di- 25 amino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane which comprises effecting M ii - reaction, in the presence of a hydrohalide acceptor, between equimolecular proportions of 2- mercapto 4,6-diamino pyrimidine and alpha, 30 beta-bis-(chloroacetamido) ethane.

GAE'I'ANO F. DALELIO.

. Certificate of Correction Patent N5. 2,324,2s3. a

GAETANO F. DALELIO.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line 26, strike out the opening parenthesis before the syllable de-" and second column, line 4-9, for that portion of the formula reading it (E t t July 13, 1943 I line 31-32, for phenlypropylene read phenylpropylene; page 3, second column,

line 35, in the formula, before the word salt strike out the bracket; page 5, first column, line 37, for chloroacetothionamido read chloroacetothionoamido; line 66,

strike out the hyphen after p' idylpage 6, second column, line 20, for n Z read n, Z; and that the said letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and-sealed this 14th day of September, A. D. 1943.

[SEAL] EENRY VAN ARSDALE,

Acting Commissioner of Patents. 

